title: Investigation of the origin and synthetic application of the pseudodilution effect for Pd-catalyzed macrocyclisations in concentrated solutions with immobilized catalysts.
abstract: Immobilized Pd-complexes allowed macrocyclisations via the Tsuji-Trost-reaction in concentrated solutions. Systematic studies suggest that the origin of this pseudodilution effect is neither film diffusion nor gel diffusion, but the reduction in conformational freedom of intermediates and intramolecular prenucleophile activation. In contrast a pseudodilution effect could not be observed for Sonogashira- and Suzuki-macrocyclisations.
authors.affiliation: Max-Planck-Institute of Molecular Physiology, Otto-Hahn-Str. 11, D-44227 Dortmund, Germany.
authors.forename: Elisabeth
authors.initials: E
authors.lastname: Brehm
authors.forename: Rolf
authors.initials: R
authors.lastname: Breinbauer
mesh_terms: D003500:Cyclization; D047028:Macrocyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D010720:Phosphines / Q000138:chemical synthesis* / Q000737:chemistry; D012996:Solutions
chemical_list: D047028:Macrocyclic Compounds; D009942:Organometallic Compounds; D010720:Phosphines; D012996:Solutions; D010165:Palladium